Aqueous systems containing nitrogen-containing, phosphorous-free carboxylic solubilizer/surfactant additives

ABSTRACT

Combinations of carboxylic solubilizers, made by reaction of an acylating agent with an N-(hydroxyl-substituted hydrocarbyl) amine and surfactants are useful in incorporating oil-soluble, water-insoluble functional additives into aqueous systems. Typical solubilizers are made by reacting an alkyl-substituted succinic anhydride containing about 12 to about 500 carbon atoms with an alkanol amine such as diethyl ethanol amine. Typical surfactants are nonionic hydrophilic surfactants such as ethoxylated phenols and ionic surfactants of both the anionic and cationic type. Typical functional additives are anti-wear, extreme pressure and load-carrying agents such as dithiophosphates. The aqueous systems formed with the aid of such combinations are useful, for example, as water-based hydraulic fluids.

REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. Ser. No. 026,384filed Apr. 2, 1979, which, in turn, is a continuation-in-part of U.S.Ser. No. 948,460 filed Oct. 4, 1978, which, in turn, is acontinuation-in-part of U.S. Ser. No. 946,294 filed Sept. 27, 1978. Thedisclosures of these prior applications are hereby incorporated byreference in this application in their entirety.

FIELD OF THE INVENTION

This invention relates to carboxylic solubilizer/surfactant combinationsand aqueous systems made from them. More particularly, the solubilizersare made from acylating agents having hydrocarbyl substituents of about12 to about 500 carbon atoms and N-(hydroxyl-substituted hydrocarbyl)amines, hereinafter, hydroxyl hydrocarbyl amines. The use of thesecombinations to prepare aqueous systems containing oil-soluble,water-insoluble functional additives is also within the scope of theinvention.

PRIOR ART

Carboxylic acid derivatives made from high molecular weight carboxylicacid acylating agents and amino compounds and their use in oil-basedlubricants are well known. See, for example, U.S. Pat. Nos. 3,216,936;3,219,666; 3,502,677; and 3,708,522.

Certain alkyl succinic acid/alkanol amine condensates have also beendescribed; see, for example, U.S. Pat. No. 3,269,946. Water-in-oilemulsions containing alkyl and alkenyl succinic acid derivatives arealso known; see, for example, U.S. Pat. Nos. 3,255,108, 3,252,908 and4,185,485.

Non-ionic hydrophilic surfactants are also well known. See, for example,the text entitled "Non-ionic Surfactants" edited by M. J. Schick,published by Marcel Dekker, Inc., New York, 1967.

Oil-soluble, water-insoluble functional additives are also well known.See, for example, the treatises by C. B. Smalheer and R. Kennedy Smith,published by Lezius-Hiles Co., Cleveland, Ohio, 1967, and by M. W.Ranney, published by Noyes Data Corp., Parkridge, New Jersey, 1973entitled "Lubricant Additives". In this connection, and throughout thespecification and appended claims, a water-insoluble functional additiveis one which is not soluble in water above a level of about 1 gram per100 milliliters of water at 25° but is soluble in mineral oil to theextent of at least one gram per liter at 25°.

BACKGROUND OF THE INVENTION

For many decades it has been a common practice to improve the propertiesof hydrocarbyl oil-based lubricants and fuels through the use ofoil-soluble, water-insoluble functional additives. These additivesimprove the oil's, for example, load-carrying and extreme pressureproperties. In recent times, the increasing cost and scarcity ofpetroleum has made it increasingly desirable to replace oil-basedcompositions with aqueous systems where ever possible. Other benefitscan also flow from such replacements such as decreased fire hazard andenvironmental pollution problems. In many cases, however, it is notfeasible to make such replacements because the aqueous systems cannot bemodified in their properties so as to perform to the same high degree astheir oil-based counterparts do. For example, it has been oftendifficult and even impossible to replace certain oil-based hydraulicfluids with water-based fluids even though the desirability of doing sois evident.

It has now been found that through the use of the carboxylicsolubilizer/surfactant combinations of the present invention, it ispossible to incorporate in aqueous systems, water-insoluble additiveswhich enable the systems to be useful, for example, as hydraulic fluids.

Therefore, it is an object of this invention to provide carboxylicsolubilizer/surfactant combinations which are useful in preparingaqueous concentrates and systems which can be used to replace certainoil-based compositions of the prior art. Other objects and advantages ofthe invention will be apparent upon the study of the followingspecification and claims.

BRIEF DESCRIPTION OF THE INVENTION

This invention comprises a composition comprising the combination of (A)at least one nitrogen-containing, phosphorus-free carboxylic solubilizermade by reaction of (A) (I) at least one carboxylic acid acylating agenthaving at least one hydrocarbyl-based substituent of at least about 12to about 500 carbon atoms with (A) (II) at least one (a)N-(hydroxyl-substituted hydrocarbyl) amine, (b) hydroxyl-substitutedpoly(hydrocarbyloxy) analog of said amine or (c) mixtures of (a) and(b); with (B) at least one surfactant.

The invention also includes aqueous systems comprising at least about40% of water and the afore-described combination with the proviso thatsaid system contains less than about 15% hydrocarbyl oil. Such aqueouscompositions encompass both concentrates containing about 40% to about70% water and water-based functional fluids made from such concentrateswith water where the ratio of water to concentrate is in the range ofabout 80:20 to about 99:1 and water-based functional fluids made fromsaid combination and water wherein the water to combination ratio is inthe range of about 80:20 to 99:1 (said ratios being by weight).

Methods for preparing aqueous systems containing (C) at least oneoil-soluble, water-insoluble functional additive which comprises thesteps of:

(1) mixing the afore-described combination with said functional additive(C) to form a dispersion/solution; optionally

(2) combining said dispersion/solution with water to form saidconcentrate with the proviso that there is present less than 15%hydrocarbyl oil present; and/or optionally

(3) diluting said concentrate or dispersion/solution with water whereinthe total amount of water used is in the amount required to provide thedesired concentration of said functional additive (C) in water;

are within the scope of the invention. Alternatively, the amount ofwater used in step (2) or (3) can be such that the functional fluid ismade directly without going through the separate step of forming aconcentrate.

DETAILED DESCRIPTION OF THE INVENTION

The carboxylic acid acylating agent, (A) (I).

The acylating agent used in making the solubilizers (A) of the presentinventive combination are well known to those of skill in the art andhave been found to be useful as additives for lubricants and fuels andas intermediates for preparing the same. See, for example, the followingU.S. Pat. Nos. which are hereby incorporated by reference for theirdisclosures relating to carboxylic acid acylating agents: 3,219,666;3,272,746; 3,381,022; 3,254,025; 3,278,550; 3,288,714; 3,271,310;3,373,111; 3,346,354; 3,272,743; 3,374,174; 3,307,928; and 3,394,179.

Generally, these carboxylic acid acylating agents are prepared byreacting an olefin polymer or chlorinated analog thereof with anunsaturated carboxylic acid or derivative thereof such as acrylic acid,fumaric acid, maleic anhydride and the like. Often they arepolycarboxylic acylating agents such as hydrocarbyl-substituted succinicacids and anhydrides. These acylating agents have at least onehydrocarbyl-based substituent of about 12 to about 500 carbon atoms.Generally, this substituent has an average of about 20, typically 30, toabout 300 carbon atoms; often it has an average of about 50 to about 250carbon atoms.

As used herein, the terms "hydrocarbon-based", "hydrocarbon-basedsubstituent" and the like denote a substituent having a carbon atomdirectly attached to the remainder of the molecule and havingpredominantly hydrocarbyl character within the context of thisinvention. Such substituents include the following:

(1) hydrocarbon substituents, that is, aliphatic (e.g., alkyl oralkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents,aromatic-, aliphatic- and alicyclic-substituted aromatic nuclei and thelike as well as cyclic substituents wherein the ring is completedthrough another portion of the molecule (that is, any two indicatedsubstituents may together form an alicyclic radical);

(2) substituted hydrocarbon substituents, that is, those substituentscontaining non-hydrocarbon radicals which, in the context of thisinvention, do not alter the predominantly hydrocarbyl substituent; thoseskilled in the art will be aware of such radicals (e.g., halo(especially chloro and fluoro)), alkoxyl, mercapto, alkylmercapto,nitro, nitroso, sulfoxy, etc.;

(3) hetero substituents, that is, substituents which will, while havingpredominantly hydrocarbyl character within the context of thisinvention, contain other than carbon present in a ring or chainotherwise composed of carbon atoms. Suitable heteroatoms will beapparent to those of skill in the art and include, for example, sulfur,oxygen, nitrogen and such substituents as e.g., pyridyl, furanyl,thiophenyl, imidazolyl, etc., are exemplary of these heterosubstituents.

In general, no more than about three radicals or heteroatoms andpreferably no more than one, will be present for each ten carbon atomsin the hydrocarbon-based substituents. Typically, there will be no suchradicals or heteroatoms in the hydrocarbon-based substituent and itwill, therefore, be purely hydrocarbyl.

In general, the hydrocarbon-based substituents present in the acylatingagents used in this invention are free from acetylenic unsaturation;ethylenic unsaturation, when present will generally be such that thereis no more than one ethylenic linkage present for every tencarbon-to-carbon bonds in the substituent. The substituents are oftencompletely saturated and therefore contain no ethylenic unsaturation.

As noted above, the hydrocarbon-based substituents present in theacylating agents of this invention may be derived from olefin polymersor chlorinated analogs thereof. The olefin monomers from which theolefin polymers are derived are polymerizable olefins and monomerscharacterized by having one or more ethylenic unsaturated group. Theycan be monoolefinic monomers such as ethylene, propylene, butene-1,isobutene and octene-1 or polyolefinic monomers (usually di-olefinicmonomers such as butadiene-1,3 and isoprene). Usually these monomers areterminal olefins, that is, olefins characterized by the presence of thegroup >C═CH₂. However, certain internal olefins can also serve asmonomers (these are sometimes referred to as medial olefins). When suchmedial olefin monomers are used, they normally are employed incombination with terminal olefins to produce olefin polymers which areinterpolymers. Although the hydrocarbyl-based substituents may alsoinclude aromatic groups (especially phenyl groups and lower alkyl and/orlower alkoxy-substituted phenyl groups such as para(tertiarybutyl)phenyl groups) and alicyclic groups such as would be obtained frompolymerizable cyclic olefins or alicyclic-substituted polymerizablecyclic olefins. The olefin polymers are usually free from such groups.Nevertheless, olefin polymers derived from such interpolymers of both1,3-dienes and styrenes such as butadiene-1,3 and styrene orpara(tertiary butyl)styrene are exceptions to this general rule.

Generally the olefin polymers are homo- or interpolymers of terminalhydrocarbyl olefins of about two to about 16 carbon atoms. A moretypical class of olefin polymers is selected from that group consistingof homo- and interpolymers of terminal olefins of two to six carbonatoms, especially those of two to four carbon atoms.

Specific examples of terminal and medial olefin monomers which can beused to prepare the olefin polymers from which the hydrocarbon-basedsubstituents are derived include ethylene, propylene, butene-1,butene-2, isobutene, pentene-1, hexene-1, heptene-1, octene-1, nonene-1,decene-1, pentene-2, propylene tetramer, diisobutylene, isobutylenetrimer, butadiene-1,2, butadiene-1,3, pentadiene-1,2, pentadiene-1,3,isoprene, hexadiene-1,5, 2-chlorobutadiene-1,3, 2-methylheptene-1,3-cyclohexylbutene-1, 3,3-dimethylpentene-1, styrenedivinylbenzene,vinylacetate allyl alcohol, 1-methylvinylacetate, acrylonitrile,ethylacrylate, ethylvinylether and methylvinylketone. Of these, thepurely hydrocarbyl monomers are more typical and the terminal olefinmonomers are especially typical.

Often the olefin polymers are poly(isobutene)s such as obtained bypolymerization of a C₄ refinery stream having a butene content of about35 to about 75 percent by weight and an isobutene content of about 30 toabout 60 percent by weight in the presence of a Lewis acid catalyst suchas aluminum chloride or boron trifluoride. These polyisobutenes containpredominantly (that is, greater than 80% of the total repeat units)isobutene repeat units of the configuration ##STR1##

Typically, the hydrocarbyl-based substituent in the carboxylic acidacylating agent as used in the present invention is a hydrocarbyl, alkylor alkenyl group of about 12 to about 500 carbon atoms which can berepresented by the indicia "hyd". Useful acylating agents includesubstituted succinic acid agents containing hydrocarbyl-basedsubstituents of about 30-500 carbon atoms.

Often the agents (A) (I) used in making the solubilizers (A) aresubstituted succinic acids or derivatives thereof which can berepresented by the formula: ##STR2## Such succinic acid acylating agentscan be made by the reaction of maleic anhydride, maleic acid, or fumaricacid with the afore-described olefin polymer, as is shown in the patentscited above. Generally, the reaction involves merely heating the tworeactants at a temperature of about 150° to about 200°. Mixtures of theafore-said polymeric olefins, as well as mixtures of unsaturated mono-and dicarboxylic acids can also be used.

The N-(hydroxyl-substituted hydrocarbyl) amine, (A) (II)

The hydroxyl hydrocarbyl amines of the present invention generally haveone to about four, typically one to about two hydroxyl groups permolecule. These hydroxyl groups are each bonded to a hydrocarbyl groupto for a hydroxyl-substituted hydrocarbyl group which, in turn, isbonded to the amine portion of the molecule. TheseN-(hydroxyl-substituted hydrocarbyl) amines can be monoamines orpolyamines and they can have a total of up to about 40 carbon atoms;generally they have a total of about 20 carbon atoms. Typically,however, they are monoamines containing but a single hydroxyl group.These amines can be primary, secondary or tertiary amines while theN-(hydroxyl-substituted hydrocarbyl) polyamines can have one or more ofany of these types of amino groups. Mixtures of two or more of any ofthe afore-described amines (A) (II) can also be used to make thecarboxylic solubilizer (A).

Specific examples N-(hydroxyl-substituted hydrocarbyl)amines suitablefor use in this invention are the N-(hydroxy-lower alkyl)amines andpolyamines such as 2-hydroxyethylamine, 3-hydroxybutylamine,di-(2-hydroxyethyl)amine, tri-(2-hydroxyethyl)amine,di-(2-hydroxypropyl)amine, N,N,N'-tri-(2-hydroxyethyl)ethylenediamine,N,N,N',N'-tetra(2-hydroxyethyl)ethylenediamine,N-(2-hydroxyethyl)piperazine, N,N'-di-(3-hydroxypropyl)piperazine,N-(2-hydroxyethyl) morpholine, N-(2-hydroxyethyl)-2-morpholinone,N-(2-hydroxyethyl)-3-methyl-2-morpholinone,N-(2-hydroxypropyl)-6-methyl-2-morpholinone,N-(2-hydroxyethyl)-5-carbethoxy-2-piperidone,N-(2-hydroxypropyl)-5-carbethoxy-2-piperidone,N-(2-hydroxyethyl)-5-(N-butylcarbamyl)-2-piperidone,N-(2-hydroxyethyl)piperidine, N-(4-hydroxybutyl) piperidine,N,N-di-(2-hydroxyethyl)glycine, and ethers thereof with aliphaticalcohols, especially lower alkanols, N,N-di(3-hydroxypropyl)glycine, andthe like.

Further amino alcohols are the hydroxy-substituted primary aminesdescribed in U.S. Pat. No. 3,576,743 by the general formula

    R.sub.a --NH.sub.2

where R_(a) is a monovalent organic radical containing at least onealcoholic hydroxy group, according to this patent, the total number ofcarbon atoms in R_(a) will not exceed about 20. Hydroxy-substitutedaliphatic primary amines containing a total of up to about 10 carbonatoms are useful. Generally useful are the polyhydroxy-substitutedalkanol primary amines wherein there is only one amino group present(i.e., a primary amino group) having one alkyl substituent containing upto 10 carbon atoms and up to 4 hydroxyl groups. These alkanol primaryamines correspond to R_(a) NH₂ wherein R_(a) is a mono- orpolyhydroxy-substituted alkyl group. It is typical that at least one ofthe hydroxyl groups be a primary alcoholic hydroxyl group.Trismethylolaminomethane is a typical hydroxy-substituted primary amine.Specific examples of the hydroxy-substituted primary amines include2-amino-1-butanol, 2-amino-2-methyl-1-propanol,p-(betahydroxyethyl)-analine, 2-amino-1-propanol, 3-amino-1-propanol,2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol,N-(betahydroxypropyl)-N'-beta-aminoethyl)piperazine, 2-amino-1-butanol,ethanolamine, beta-(betahydroxy ethoxy)-ethyl amine, glucamine,glusoamine, 4-amino-3-hydroxy-3-methyl-1-butene (which can be preparedaccording to procedures known in the art by reacting isopreneoxide withammonia), N-3-(aminopropyl)-4(2-hydroxyethyl)-piperadine,2-amino-6-methyl-6-heptanol, 5-amino-1-pentanol,N-(beta-hydroxyethyl)-1,3-diamino propane,1,3-diamino-2-hydroxy-propane, N-(beta-hydroxyethoxyethyl)-ethylenediamine, and the like. For further description ofthe hydroxy-substituted primary amines useful as theN-(hydroxyl-substituted hydrocarbyl) amines in this invention see U.S.Pat. No. 3,576,743 which is expressly incorporated herein by referencefor its disclosure of such amines.

Typically, the amine (A) (II) is a primary, secondary or tertiaryalkanol amine or mixture thereof. Such amines can be represented,respectively, by the formulae: ##STR3## wherein each R is independentlya hydrocarbyl group of one to about eight carbon atoms orhydroxyl-substituted hydrocarbyl group of two to about eight carbonatoms and R' is a divalent hydrocarbyl group of about two to abouteighteen carbon atoms. The group --R'--OH in such formulae representsthe hydroxyl-substituted hydrocarbyl group. R' can be an acyclic,alicyclic or aromatic group. Typically, it is an acyclic straight orbranched alkylene group such as an ethylene, 1,2-propylene,1,2-butylene, 1,2-octadecylene, etc. group. Where two R groups arepresent in the same molecule they can be joined by a directcarbon-to-carbon bond or through a heteroatom (e.g., oxygen, nitrogen orsulfur) to form a 5-, 6-, 7- or 8-membered ring structure. Examples ofsuch hetrocyclic amines include N-(hydroxyl lower alkyl)-morpholines,-thiomorpholines, -piperidines, -oxazolidines, -thiazolidines and thelike. Typically, however, each R is a lower alkyl group of up to 7carbon atoms.

The amine (A) (II) can also be an ether N-(hydroxyl-substitutedhydrocarbyl)amine. These are hydroxyl-substituted poly(hydrocarbyloxy)analogs of the above-described amines (these analogs also includehydroxyl-substituted oxyalkylene analogs). Such amines can beconveniently prepared by reaction of epoxides with afore-describedamines and can be represented by the formulae: ##STR4## wherein x is anumber from 2 to about 15 and R and R' are as described above.

Polyamine analogs of these alkanol amines, particularly alkoxylatedalkylene polyamines (e.g., N,N-(diethanol)ethylene diamine) can also beused to make the solubilizers of this invention. Such polyamines can bemade by reacting alkylene amines (e.g., ethylene diamine) with one ormore alkylene oxides (e.g., ethylene oxide, octadecene oxide) of two toabout twenty carbons. Similar alkylene oxide-alkanol amine reactionproducts can also be used such as the products made by reacting theafore-described primary, secondary or tertiary alkanol amines withethylene, propylene or higher epoxides in a 1:1 or 1:2 molar ratio.Reactant ratios and temperatures for carrying out such reactions areknown to those skilled in the art.

Specific examples of alkoxylated alkylene polyamines includeN-(2-hydroxyethyl)ethylene diamine, N,N-bis(2-hycroxyethyl)-ethylenediamine, 1-(2-hydroxyethyl)piperazine, mono(hydroxypropyl)-substituteddiethylene triamine, di(hydroxypropyl)-substituted tetraethylenepentamine, N-(3-hydroxybutyl)-tetramethylene diamine, etc. Higherhomologs obtained by condensation of the above-illustrated hydroxyalkylene polyamines through amino radicals or through hydroxy radicalsare likewise useful. Condensation through amino radicals results in ahigher amine accompanied by removal of ammonia while condensationthrough the hydroxy radicals results in products containing etherlinkages accompanied by removal of water. Mixtures of two or more of anyof the aforedescribed mono- or polyamines are also useful.

Particularly useful examples of N-(hydroxyl-substitutedhydrocarbyl)amines (A) (II) include mono-, di-, and triethanol amine,diethylethanol amine, di-(3-hydroxyl propyl) amine, N-(3-hydroxyl butyl)amine, N-(4-hydroxyl butyl) amine, N,N-di-(2-hydroxyl propyl) amine,N-(2-hydroxyl ethyl) morpholine and its thio analog, N-(2-hydroxylethyl) cyclohexyl amine, N-3-hydroxyl cyclopentyl amine, o-, m- andp-aminophenol, N-(hydroxyl ethyl) piperazine, N,N'-di(hydroxyl ethyl)piperazine, and the like. Preferred amines are diethyl ethanol amine andethanol amine and mixtures thereof.

The reaction of the acylating agent (A) (I) with the hydroxyl amine (A)(II) to form the nitrogen-containing carboxylic solubilizer (A).

The reaction of the acylating agent (A) (I) with the hydroxyl amine (A)(II) can be carried out at temperatures ranging from about 30° to thedecomposition temperature of the reaction components and/or productshaving the lowest such temperature. Generally it is carried out at atemperature in the range of about 50° to about 150°; but usually at atemperature below about 100°. Often the reaction is carried out underester-forming conditions and the product thus formed is, for example, anester, salt, amide, imide, amic ester or mixture of such products. Thesalt may be an internal salt, wherein one of the carboxyl groups becomesionically bound to a nitrogen atom within the same group or it may be anexternal salt wherein the ionic salt group is formed with a nitrogenatom which is not part of the same group forming the ester group.Mixtures of acylating agents and/or mixtures of hydroxyl amines can beused.

Generally, the ratio of acylating agent to N-(hydroxyl-substitutedhydrocarbyl)amine is in the range of 0.5 to about 3 moles of amine (A)(II) per equivalent of acylating agent (A) (I). An equivalent ofacylating agent (A) (I) can be determined by dividing its molecularweight by the number of carboxyl functions present. These can usually bedetermined from the structural formula of the acylating agent orempirically through well-known titration procedures. For example, asuccinic acid anhydride or di(alkyl) ester acylating agent has anequivalent weight of one-half its molecular weight.

In addition to the acylating agent (A) (I) there may also be present inthe solubilizer-forming reaction mixture one or more lower molecularweight mono- or poly-carboxylic acid acylating agents of one to aboutless than 18 carbons such as fatty acids having 10 to about 18 carbonatoms or a tetrapropenyl-substituted succinic anhydride. In such casesthe moles of lower acylating agent present will be at least less thanthose of the acylating agent (A) (I) and the total equivalents of loweracylating agent plus acylating agent (A) (I) will still fall within theafore-described ratios.

Typical lower (MW) monocarboxylic acylating agents include saturated andunsaturated fatty acids, such as lauric acid, stearic acid, oleic acid,myristic acid, linoleic acid, and the like. Anhydrides, when available,and lower alkyl esters of these acids can also be used. Mixtures of twoor more such agents can also be successfully used. An extensivediscussion of such acids is found in Kirk-Othmer "Encyclopedia ofClaimed Technology" 2nd Edition, 1965, John Wiley & Sons, N.Y., pages811-856. Acylating agents including acetic acid, propionic acid, butyricacid, acrylic and benzoic acid as well as their anhydrides and loweralkyl esters are also useful.

Among the useful lower Mw polycarboxylic acylating agents are maleicacid, fumaric acid, itaconic acid, mesaconic acid, succinic acidphthalic acid, alkyl-substituted phthalic acids, isophtahalic acid,malonic acid, glutaric acid, adipic acid, citraconic acid, glutaconicacid, chloromaleic acid, atconic acid, scorbic acid, etc. Againanhydrides when available, and lower alkyl esters and esters of theseacids can be use as lower Mw acylating agents.

Certain substituted succinic acid and anhydride lower Mw acylatingagents can also be used. A number of these are discussed in theabove-cited Kirk-Othmer article at pages 847-849. The typical suchacylating agents can be represented by the formula: ##STR5## wherein R*is a C₁ to about a C₁₀ hydrocarbyl group. Preferably, R* is an aliphaticor alicyclic hydrocarbyl group less than 10% of its carbon-to-carbonbonds unsaturated. Examples of such groups are 4-butylcyclohexyl,di(isobutyl), decyl, etc. The production of such substituted succinicacids and their derivatives via alkylation of maleic acid or itsderivatives with a halo-hydrocarbon is well known to those of skill inthe art and need not be discussed in detail at this point.

Acid halides of the afore-described lower Mw mono- and polycarboxylicacids can be used as lower Mw acylating agents in this invention. Thesecan be prepared by the reaction of such acids or their anhydrides withhalogenating agents such as phosphorus tribromide, phosphoruspentachloride, phosphorus oxychloride, or thionyl chloride. Esters ofsuch acids can be prepared simply by the reaction of the acid, acidhalide or anhydride with an alcohol or phenolic compound. Particularlyuseful are the lower alkyl and alkenyl alcohols such as methanol,ethanol, allyl alcohol, propanol, cyclohexanol, etc. Esterificationreactions are usually promoted by the use of alkaline catalysts such assodium hydroxide or alkoxide, or an acidic catalyst such as sulfuricacid or toluene sulfonic acid.

The reaction of acylating agent and hydroxyl amine can be carried out inthe presence of a normally liquid, substantially inert, organicsolvent/diluent such as benzene, octane, and commercial mixtures such asthe various textile spirits and naphthas. Mineral oils in small amountscan also be used. Such solvent/diluents aid in temperature control,viscosity control and the like. Often, however, when the reactants aresufficiently fluid such solvent/diluents are not used and the reactionis carried out in the absence of any materials other than the acylatingagent (A) (I) and the hydroxyl amine (A) (II).

The surfactant (B)

The nitrogen-containing, phosphorus-free carboxylic solubilizers (A) ofthis invention are used in combination with at least one surfactant orwetting agent, (B). This surfactant serves to reduce the viscosity ofthe solubilizer making it more easily handled and often also aids in thedispersal of the solubilizer and functional additive in the aqueoussystem. Typically, the surfactant (B) is a hydrophilic surfactant and,generally, it has an HLB (hydrophilic-lipophilic balance) in the rangeof about 10 to about 20.

The surfactant can be of the cationic, anionic, nonionic or amphoterictype. Many such surfactants of each type are known to the art. See, forexample, McCutcheon's "Detergents and Emulsifiers", 1978, North AmericanEdition, published by McCutcheon's Division, MC Publishing Corporation,Glen Rock, New Jersey, U.S.A., particularly pages 17-33 which are herebyincorporated by reference for their disclosures in this regard.

Of these surfactants (B), non-ionic surfactants are generally used. Anumber of non-ionic surfactant types are known. Among these are thealkylene oxide-treated products, such as ethylene oxide-treated phenols,alcohols, esters, amines and amides. Ethylene oxide/propylene oxideblock copolymers are also useful non-ionic surfactants. Glycerol estersand sugar esters are also known to be non-ionic surfactants. A typicalnon-ionic surfactant class useful with the derivatives of the presentinvention are the alkylene oxide-treated alkyl phenols such as theethylene oxide alkyl phenol condensates sold by the Rohm & Haas Company.A specific example of these is Triton X-100 which contains an average of9-10 ethylene oxide units per molecule, has an HLB value of about 13.5and a molecular weight of about 628. Many other suitable non-ionicsurfactants are known; see, for example, the afore-mentionedMcCutcheon's as well as the treatise "Non-ionic Surfactants" edited byMartin J. Schick, M. Drekker Co., New York, 1967, which is herebyincorporated by reference for its disclosures in this regard.

As noted above, cationic, anionic and amphoteric surfactants can also beused in combination with the solubilizers (A) in this invention.Generally, these are all hydrophilic surfactants. Anionic surfactantscontaining negatively charged polar groups while cationic surfactantscontain positively charged polar groups. Amphoteric dispersants containboth types of polar groups in the same molecule. A general survey ofuseful surfactants is found in Kirk-Othmer Encyclopedia of ChemicalTechnology, Second Edition, Volume 19, page 507 and following (1969,John Wiley and Son, New York) and the aforementioned compilationpublished under the name of McCutcheon's. These references are bothhereby incorporated by reference for their disclosures relating tocationic, amphoteric and anionic surfactants.

Among the useful anionic surfactant types are the widely known metalcarboxylate soaps, organo sulfates, sulfonates, sulfocarboxylic acidsand their salts, and phosphates. Useful cationic surfactants includenitrogen compounds such as amine oxides and the well known quaternaryammonium salts. Amphoteric surfactants include amino acid type materialsand similar types. Various cationic, anionic and amphoteric dispersantsare available from the industry, particularly from such companies asRohm and Haas and Union Carbide Corporation, both of America. Furtherinformation about anionic and cationic surfactants also can be found inthe texts "Anionic Surfactants", Parts II and III, edited by W. M.Linfield, published by Marcel Dekker, Inc., New York, 1976 and "CationicSurfactants", edited by E. Jungermann, Marcel Dekker, Inc., New York,1976. Both of these references are incorporated by reference for theirdisclosures in this regard.

The oil-soluble, water-insoluble functional additive (C)

The solubilizer (A)/surfactant (B) combinations of the present inventionare useful in dispersing oil-soluble, water-insoluble functionaladditives (C) in aqueous systems.

The functional additives (C) that can be dispersed with the combinationsof this invention are generally well known to those of skill in the artas mineral oil and fuel additives. They generally are not soluble inwater beyond the level of one gram per 100 milliliters at 25°, and oftenare less soluble than that. Their mineral oil solubility is generallyabout at least one gram per liter at 25°.

Among the functional additives (C) are extreme pressure agents,corrosion and oxidation inhibiting agents, such as chlorinated aliphatichydrocarbons (e.g., chlorinated waxes), and organic sulfides andpolysulfides (e.g., benzyl disulfide, bis(chlorobenzyl)disulfide,dibutyltetrasulfide, sulfurized methyl esters of fatty acid, sulfurizedalkyl phenols, sulfurized dipentenes and sulfurized terpenes).

The functional additive (C) can also be chosen fromphosphorus-containing materials and include phosphosulfurizedhydrocarbons such as the reaction product of a phosphorus sulfide withterpenes or methyl fatty esters, phosphorus esters such as the aciddihydrocarbyl and trihydrocarbyl phosphites such as dibutyl phosphites,diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite,dipentyl phenyl phosphite, tridecyl phosphite, distearyl phosphite,dimethyl naphthyl phosphite, oleyl 4-pentylphenyl phosphite,polypropylene (molecular weight 500)-substituted phenyl phosphite,diisobutyl-substituted phenyl phosphite; metal thiocarbamates, such aszinc dioctyldithiocarbamate, and barium heptylphenyl dithiocarbamate;Group II metal salts of acid phosphate and thiophosphate hydrocarbylester such as zinc dicyclohexyl phosphorodithioate, zincdioctylphosphorodithioate, barium di(heptylphenol)-phosphorodithioate,cadmium dinonylphosphorodithioate, and the zinc salt of aphosphorodithioic acid produced by the reaction of phosphoruspentasulfide with an equimolar mixture of isopropyl alcohol and n-hexylalcohol.

Other types of suitable functional additives (C) include carbamates andtheir thioanalogs, overbased and gelled overbased carboxylic, sulfonicand phosphorus acid salts, high molecular weight carboxylate esters, andnitrogen-containing modifications thereof, high molecular weightphenols, condensates thereof; high molecular weight amines andpolyamines; high molecular weight carboxylic acid/amino compoundproducts, etc. Further descriptions of these and other suitablefunctional additives (C) can be found in the afore-mentioned treatises"Lubricant Additives" which are hereby incorporated by reference fortheir disclosures in this regard.

Generally, the combination compositions of this invention comprise about25 to about 75 weight percent solubilizer (A) and about 75 to about 25weight percent surfactant (B). Typically they comprise from about 40 toabout 60 weight percent solubilizer and about 10 to about 60 weightpercent surfactant. When present, the oil-soluble, water-insolublefunctional additives (C) comprise about 10 to about 50 weight percent.Sometimes these combinations will contain up to about 50% oil; generallyup to about 25% oil. This oil, if present, usually serves to reduce thecombination's viscosity and thus makes it more convenient to handle.These combinations are generally substantially non-aqueous; that is,they contain less than about 40% water. As such, they can often benon-aqueous concentrates containing (A) solubilizer, (B) surfactant, andoptionally (C) functional additive and/or oil. The oil is hydrocarbyl orsynthetic (ester, etc.).

The aqueous systems of the present invention contain at least about 40%water and less than about 15% hydrocarbyl oil. The relative amounts ofsolubilizers (A), surfactants (B) and water-insoluble functionaladditives (C) (if the latter is present), are within the ranges statedabove so that if the water is withdrawn from the system these amountswill be within these ranges. Generally these aqueous systems containless than about 5% hydrocarbyl oil. Often they are substantiallyoil-free (i.e., less than 2% oil).

Additive concentrates containing the combination compositions of thisinvention can be either aqueous or substantially non-aqueous dependingupon whether they contain more or less than 40% (by weight) water.Aqueous concentrates for the formulation of water-based functionalfluids contain about 40% to about 70% water; generally about 40% toabout 65% water. Such concentrates often also contain at least oneoil-soluble, water-insoluble functional additive (C). The functionaladditive's concentration is such that, if the water were removed, itwould fall within the range set forth above for the combinationcomposition themselves. Typically these oil-soluble, water-insolublefunctional additives (C) are an anti-wear, extreme pressure, and/orload-carrying agent, such as the well-known metal salts of acidphosphates and acid thiophosphate hydrocarbyl esters. An example of thelatter are the well-known zinc di(alkyl) or di(aryl) dithiophosphates.

The substantially non-aqueous concentrates are analogous to theafore-described aqueous concentrates except they contain less water(i.e., less than 40%) and proportionately more of the other ingredients.

The substantially non-aqueous and aqueous concentrates of this inventioncan both be converted to water-based (i.e., aqueous) functional fluidsby the dilution with water. This dilution is usually done by standardmixing techniques. This is often a convenient procedure since theconcentrate can be shipped to the point of use before the water isadded. Thus, the cost of shipping a substantial amount of the water inthe final water-based functional fluid is saved. Only the waternecessary to formulate the concentrate (which is determined primarily byease of handling and convenience factors), need be shipped.

Generally these water-based fluids are made by diluting theafore-described substantially non-aqueous and aqueous concentrates withwater, wherein the ratio of water to concentrate is in the range ofabout 80:20 to about 99:1 by weight. As can be seen when dilution iscarried out within these ranges, the final water-based functional fluidcontains, at most, an insignificant amount of hydrocarbyl oil. Thisclearly distinguishes them from soluble oils.

Also included within the invention are methods for preparing aqueoussystems, including both aqueous concentrates and water-based functionalfluids, containing (C) at least one oil-soluble, water-insolublefunctional additive. These methods comprise the steps of:

(1) mixing the combination of solubilizer and surfactant with at leastone functional additive (C) to form a dispersion/solution; optionally

(2) combining said dispersion/solution with water to form said aqueousconcentrates and, with the proviso there is less than about 15%hydrocarbyl oil present, either simultaneously or sequentially, ifdesired; and/or

(3) diluting said dispersion/solution or concentrate with water whereinthe total amount of water used is in the amount required to provide thedesired concentration of said functional additive (C) in saidconcentrate or said water-based functional fluids.

These mixing steps are carried out using conventional equipment andgenerally at room or slightly elevated temperatures, usually below 100°C. and often below 50° C. The total amounts of (A), (B) and (C) arewithin the ranges set forth above. As noted above, the non-aqueous oraqueous concentrate can be formed and then shipped to the point of usewhere it is diluted with water to form the desired water-basedfunctional fluid. In other instances the finished water-based functionalfluid can be formed directly in the same equipment used to form theconcentrate or dispersion/solution.

The following are specific examples of the present invention. In theseexamples all parts, percentages and ratios are by weight and alltemperatures are in degrees Celsius unless expressly stated to thecontrary, as is the case throughout this specification and appendedclaims.

EXAMPLE 1(A)

To 6720 parts of a poly(isobutene)-substituted succinic anhydride(having a molecular weight of 1120), heated to 90° with stirring, isslowly added over 1.5 hours 702 parts of diethyl ethanol amine. Thisintermediate mixture is heated for an additional 0.5 hour at 90° andthen 366 parts of monoethanol amine is added. The mixture is held at 90°for a final 0.5 hour and cooled to provide the desired product.

EXAMPLE 1(B)

A mixture is prepared containing 3600 parts of the afore-describedproduct, 2160 parts of a naphthenic neutral hydrocarbyl oil having aviscosity of 100 SSU at 100° F., 1440 parts of Triton X-100 and 1800parts of a commercially available load-carrying additive which is thezinc salt of an acid O,O'-di(alkyl-substituted phenyl) dithiophosphate.This mixture is heated to 90° and stirred for 0.5 hour. This concentratecan be diluted with water in the ratio of 80 parts water:20 partsconcentrate to provide a water-based hydraulic fluid.

EXAMPLE 2(A)

To a charge of 224 parts of the succinic anhydride discribed in Example1(A), heated in a resin kettle with stirring at about 90°, is slowlyadded over a two-hour period 468 parts of diethyl ethanol amine. Heatingis continued for an additional hour at 90°. The desired solubilizer is aviscous, brownish liquid at room temperature.

EXAMPLE 2(B)

A charge of 4000 parts of the solubilizer, 1000 parts of Triton X-100and 1667 parts of the commercial anti-wear, load-carrying agentdescribed in Example 1(B) is mixed well at 60° to provide a concentrateuseful in formulating waterbased hydraulic fluids.

EXAMPLE 3(A)

A mixture is formed by coupling 30 parts of the oil of Example 2(B), 40parts of the product of Example 1(A) and 30 parts of a commercialsurfactant sold under the name Minfoam 2× by the Union CarbideCorporation and identified as a modified linear alcohol ethoxylate iscombined to form a mixture.

When 3 parts of this mixture is combined with 7 parts of water andagitated, an aqueous system is formed which shows none of thecharacteristics of an emulsion. The system is not opaque and there is noobvious phase separation.

EXAMPLE 3(B)

Nine parts of the mixture of Example 3(A) is combined with 1 part of acommercial high molecular weight, oil-solublepoly(isobutene)-substituted succinic acid/polyol ester dispersant, awell-known functional additive. This combination is then combined withwater in the ratio of 3 parts combination to 7 parts water. Afteragitation the system thus formed, again, does not appear to be anemulsion and is not opaque nor does it show signs of phase separation.

EXAMPLE 4(A)

A mixture of 4200 parts of the solubilizer described in Example 1(A),1680 parts of the surfactant described in Example 1(B) and 2520 parts ofa zinc di(isooctyl) dithiophosphate is stirred for one hour at 60° andthen stored for an additional hour to form a combination.

EXAMPLE 4(B)

Eight thousand parts of the combination of Example 4(A) is mixed for twohours with 12,000 parts water at a temperature of about 38° to form anaqueous system. This system is then poured through a 30 mesh screen togive an aqueous concentrate having a density of 8.39 pounds per gallon.It can be combined further with water to provide a water-based hydraulicfluid.

EXAMPLE 5

A combination is prepared in essentially the same fashion as describedin Example 4(A) and (B) from 20 parts of the solubilizer described inExample 1(A), 8 parts of the surfactant described in Example 1(B), 8parts of a commercial anti-wear and load-carrying agent, which is a zincsalt of O,O'-di(isooctyl)dithiophosphoric acid, and 4 parts of acommercial anti-wear agent which is an isobutene-derived polysulfide.This is combined with 60 parts of water to form an aqueous system whichis an aqueous concentrate. This system can be diluted in the ratio of 5parts per weight system to 95 parts by weight water, to make awater-based hydraulic fluid.

EXAMPLE 6

A mixture of 220 parts of the product of Example 1(A), 120 parts of thezinc dithiophosphate of Example 4(A) and 80 parts of sodium lauryl ethersulfate (sold by Alcolac, Inc., under the trade name Sipon ESY) isprepared. To this stirred mixture at 40°-50° is slowly added 565 partswater and then 15 parts aminopropyl morpholine. The mixture is stirredwell to provide the desired concentrate.

EXAMPLE 7

A mixture is prepared of 220 parts of the product of Example 1(A), 120parts of the zinc dithiophosphate of Example 4(A) and 80 parts of anethoxylated oleyl amine (sold under the trade name "Ethomeen O/15" byThe Armour Corporation). The mixture is heated to 40°-50° and 20 partsby weight aminopropyl morpholine is slowly added; then 560 parts wateris added and the mixture stirred for approximately 0.75 hours to yield awell-mixed concentrate.

Each of the concentrates of Examples 6 and 7 are mixed with water in theweight ratio of 95 parts water to 5 parts concentrate to provide aqueoussystems. These systems produce ring-wear rates of 13.1 milligrams/perhour and 7.9 milligrams/per hour when evaluated in a 50 hour vane pumptest.

The solubilizer/surfactant combinations of the present invention canalso be used to incorporate water into hydrocarbyl fuels such as dieselfuel. This is often desired to reduce the particulate matter in theexhaust of engines using such fuels. It is believed that one mechanismby which this occurs is through the formation of steam in diesel fueldroplets as they are sprayed into the combustion chamber. This steamformation aids in dispersing the diesel fuel so that it is morecompletely burned to carbon dioxide and water. Generally thesefuel/water combinations contain about 0.2% to about 25% solubilizer plussurfactant combination, about 2% to about 20% water with the balancebeing fuel and other conventional additives. It is believed that suchsystems are micro- or macro-emulsions. It is found that when suchwater/fuel emulsions are used in a diesel engine, a reduction of about7% to about 10% in exhaust particulates results.

What is claimed is:
 1. A composition comprising a continuous aqueousphase and the combination of (A) at least one nitrogen-containing,phosphorous-free carboxylic solubilizer and (B) at least one surfactantin said aqueous phase, said solubilizer (A) being made by the reactionof (A)(I) at least one acylating agent represented by the formula:##STR6## wherein hyd is a hydrocarbon-based substituent of about 30 toabout 500 carbon atoms with (A)(II) at least one (a)N-(hydroxyl-substituted hydrocarbyl) amine, (b) hydroxyl-substitutedpoly(hydrocarbyloxy) analog of said amine or (c) mixtures of (a) and(b), the ratio of components (A)(II) to (A)(I) being in the range ofabout 0.5 to about 3 moles of component (A)(II) per equivalent ofcomponent (A)(I).
 2. The composition of claim 1 wherein hyd has about 30to about 300 carbon atoms.
 3. The composition of claim 1 wherein hyd hasabout 50 to about 250 carbon atoms.
 4. The composition of claim 1wherein hyd is an alkyl or an alkenyl group.
 5. The composition of claim1 wherein hyd is poly (isobutene).
 6. The composition of claim 1 whereinthe amine (A)(II) has from 1 to 4 hydroxyl groups per molecule bonded toa hydrocarbyl group, said hydrocarbyl group being bonded to the amineportion of the molecule.
 7. The composition of claim 1 wherein the amine(A)(II) is a monoamine.
 8. The composition of claim 1 wherein the amine(A)(II) is a polyamine.
 9. The composition of claim 1 wherein the amine(A)(II) contains up to about 40 carbon atoms.
 10. The composition ofclaim 1 wherein the amine (A)(II) is a primary, secondary or tertiaryalkanol amine of up to about 40 carbon atoms.
 11. The composition ofclaim 1 wherein the amine (A)(II) is a mixture of at least two alkanolamines of up to about 40 carbon atoms each.
 12. The composition of claim1 wherein the amine (A)(II) is a hydroxy-substituted primary amine ofthe formula

    R.sub.a --NH.sub.2

wherein R_(a) is a monovalent organic radical containing at least onehydroxy group, the total number of carbon atoms in R_(a) not exceedingabout
 20. 13. The composition of claim 12 wherein the total number ofcarbon atoms in R_(a) does not exceed
 10. 14. The composition of claim12 wherein R_(a) contains up to 4 hydroxyl groups.
 15. The compositionof claim 12 R_(a) is a monohydroxy-substituted alkyl group.
 16. Thecomposition of claim 1 wherein the amine (A)(II) is selected from thegroup consisting of (a) primary, secondary and tertiary alkanol amineswhich can be represented correspondingly by the formulae: ##STR7## (b)hydroxyl-substituted oxyalkylene analogs of said alkanol aminesrepresented by the formulae: ##STR8## wherein each R is independently ahydrocarbyl group of one to about 8 carbon atoms or hydroxyl-substitutedhydrocarbyl group of 2 to about 8 carbon atoms and R' is a divalenthydrocarbyl group of two to about 18 carbon atoms, and (c) mixtures oftwo or more thereof.
 17. The composition of claim 1 wherein the amine(A)(II) is a mixture of diethylethanolamine and ethanolamine.
 18. Thecomposition of claim 1 wherein the surfactant (B) is a non-ionic,cationic, or anionic hydrophilic surfactant.
 19. The composition ofclaim 1 wherein the surfactant (B) is an anionic surfactant.
 20. Thecomposition of claim 1 wherein the surfactant (B) is a hydrophilicsurfactant having an HLB value of about 10 to about
 20. 21. Thecomposition of claim 1 wherein the surfactant (B) is an ethoxylatedalkyl phenol.
 22. The composition of claim 1 wherein the surfactant (B)is selected from the group consisting of metal carboxylate soaps, organosulfates, sulfonates, sulfocarboxylic acids and/or their salts, andphosphates.
 23. The composition of claim 1 wherein there is also presentin the solubilizer forming reaction mixture at least one lower molecularweight carboxylic acylating agent of 1 to about 18 carbon atoms inaddition to the acylating agent (A)(I).
 24. The composition of claim 23wherein said lower molecular weight acylating agent is a fatty acid of10 to 18 carbon atoms.
 25. The composition of claim 23 wherein saidlower molecular weight acylating agent is a low molecular weight alkylor alkenyl succinic acid.
 26. The composition of claim 23 wherein saidlower molecular weight acylating agent is tetrapropenyl succinicanhydride.
 27. The composition of claim 1 wherein there is also presentin the solubilizer forming reaction mixture at least one lower molecularweight substituted succinic acid or anhydride in addition to theacylating agent (A)(I), said lower molecular weight succinic acid oranhydride being represented by the formulae: ##STR9## wherein R* is ahydrocarbyl group of about 1 to about 10 carbon atoms.
 28. Thecomposition of claim 1 wherein there is also present in solubilizerforming reaction mixture in addition to the acylating agent (A)(I) atleast one acid halide of a lower molecular weight carboxylic acidacylating agent of about 1 to about 18 carbon atoms.
 29. The compositionof any one of claims 1-28 with (C) at least one oil-soluble,water-insoluble functional additive dispersed in said aqueous phase. 30.The composition of any one of claims 1-28 with at least about 40% waterand less than about 15% hydrocarbyl oil.
 31. The composition of any oneof claims 1-28 with about 40% to about 70% water, less than about 15%hydrocarbyl oil, said composition being an aqueous concentrate.
 32. Thecomposition of any one of claims 1-28 with about 40% to about 70% water,less than about 15% hydrocarbyl oil, and (C) at least one oil-soluble,water-insoluble functional additive, said composition being an aqueousconcentrate.
 33. The composition of claim 29 wherein the additive (C) isan anti-wear, extreme-pressure agent and/or load-carrying agent.
 34. Thecomposition of claim 29 wherein the additive (C) is a metal salt of anacid phosphate or acid thiophosphate hydrocarbyl ester.
 35. Awater-based functional fluid made by diluting the composition of claim31 with water wherein the ratio of water to concentrate is in the rangeof about 80:20 to about 99:1.
 36. A water-based functional fluid made bydiluting the composition of claim 32 with water wherein the ratio ofwater to concentrate is in the range of about 80:20 to about 99:1. 37.The composition of claim 29 wherein the functional additive (C) is atleast one phosphorus- and/or sulfur-containing additive.
 38. A methodfor preparing aqueous systems, including both aqueous concentrates andwater-based functional fluids, containing (C) at least one oil-soluble,water-insoluble, functional additive which comprises the steps of:(1)mixing the composition of any one of claims 1-28 with said functionaladditive (C) to form a dispersion/solution; optionally (2) combiningsaid dispersion/solution with water to form said concentrate; and/oroptionally (3) diluting said concentrate or dispersion/solution withwater wherein the total amount of water used is in the amount requiredto provide the desired concentration of said functional additive (C) insaid water-based functional fluid.